Oxygen and sulphur heterocycles derived from chloroaldehydes

 

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dc.contributor.advisor Irving, H M N H en_ZA
dc.contributor.author Archer, Steven James en_ZA
dc.date.accessioned 2016-02-15T07:15:58Z
dc.date.available 2016-02-15T07:15:58Z
dc.date.issued 1984 en_ZA
dc.identifier.citation Archer, S. 1984. Oxygen and sulphur heterocycles derived from chloroaldehydes. University of Cape Town. en_ZA
dc.identifier.uri http://hdl.handle.net/11427/17043
dc.description Includes bibliography. en_ZA
dc.description.abstract Chloral may be trimerised, tetramised and polymerised, to form parachloral, metachloral and polychloral, respectively. Parachloral has two isomers: the cis-isomer and the trans-isomer. An analysis of the conformational equilibria occuring in solution, was carried out for trans-parachloral, using the techniques of dipole moment measurement and infrared and nmr spectroscopy Both isomers exist in cis-chair conformations, but differ in the chirality of the β-carbon atoms in the side chains. A comparison of the mass spectral fragmentations of parachloral and parabutylchloral is included. The structure of a related five-membered heterocycle, trans-chloralide was also investigated by x-ray crystallography. The cis-isomer of chloralide is reported for the first time. The unusual mechanism, in which carbon monoxide acts as nucleophile, by which chloralide is formed from chloral and fuming sulphuric acid, has been elucidated using 13C-labelling. The dehydrochlorination of chloralide under unexpected conditions, is also discussed. The isomerism in a series sulphur-containing analogues of parachloral was investigated. 2-Trans-dithioparachloral and its dehydrochlorination product, were shown by x-ray crystallography. A comparative study of the effects on the 1H and 13Cnmr spectra, of structural changes in these six-membered heterocycles, is discussed at length. Some introductory preparative work was done, regarding the potential use of 1,3,5-trithiane 1,3,5-trioxides with three axial sulphoxide groups, as terdentate ligands. en_ZA
dc.language.iso eng en_ZA
dc.subject.other Chemistry en_ZA
dc.title Oxygen and sulphur heterocycles derived from chloroaldehydes en_ZA
dc.type Doctoral Thesis
uct.type.publication Research en_ZA
uct.type.resource Thesis en_ZA
dc.publisher.institution University of Cape Town
dc.publisher.faculty Faculty of Science en_ZA
dc.publisher.department Department of Chemistry en_ZA
dc.type.qualificationlevel Doctoral
dc.type.qualificationname PhD en_ZA
uct.type.filetype Text
uct.type.filetype Image
dc.identifier.apacitation Archer, S. J. (1984). <i>Oxygen and sulphur heterocycles derived from chloroaldehydes</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/17043 en_ZA
dc.identifier.chicagocitation Archer, Steven James. <i>"Oxygen and sulphur heterocycles derived from chloroaldehydes."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 1984. http://hdl.handle.net/11427/17043 en_ZA
dc.identifier.vancouvercitation Archer SJ. Oxygen and sulphur heterocycles derived from chloroaldehydes. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 1984 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/17043 en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Archer, Steven James AB - Chloral may be trimerised, tetramised and polymerised, to form parachloral, metachloral and polychloral, respectively. Parachloral has two isomers: the cis-isomer and the trans-isomer. An analysis of the conformational equilibria occuring in solution, was carried out for trans-parachloral, using the techniques of dipole moment measurement and infrared and nmr spectroscopy Both isomers exist in cis-chair conformations, but differ in the chirality of the β-carbon atoms in the side chains. A comparison of the mass spectral fragmentations of parachloral and parabutylchloral is included. The structure of a related five-membered heterocycle, trans-chloralide was also investigated by x-ray crystallography. The cis-isomer of chloralide is reported for the first time. The unusual mechanism, in which carbon monoxide acts as nucleophile, by which chloralide is formed from chloral and fuming sulphuric acid, has been elucidated using 13C-labelling. The dehydrochlorination of chloralide under unexpected conditions, is also discussed. The isomerism in a series sulphur-containing analogues of parachloral was investigated. 2-Trans-dithioparachloral and its dehydrochlorination product, were shown by x-ray crystallography. A comparative study of the effects on the 1H and 13Cnmr spectra, of structural changes in these six-membered heterocycles, is discussed at length. Some introductory preparative work was done, regarding the potential use of 1,3,5-trithiane 1,3,5-trioxides with three axial sulphoxide groups, as terdentate ligands. DA - 1984 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1984 T1 - Oxygen and sulphur heterocycles derived from chloroaldehydes TI - Oxygen and sulphur heterocycles derived from chloroaldehydes UR - http://hdl.handle.net/11427/17043 ER - en_ZA


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